CN103380180A

CN103380180A - Methods of solubilizing milling media in pigment particle dispersions

Info

Publication number: CN103380180A
Application number: CN2011800674564A
Authority: CN
Inventors: 马克·奥塔兰诺
Original assignee: Sun Chemical Corp
Current assignee: Sun Chemical Corp
Priority date: 2010-12-13
Filing date: 2011-12-13
Publication date: 2013-10-30
Anticipated expiration: 2031-12-13
Also published as: CN103380180B; EP2652048A1; WO2012082741A8; JP2013545878A; WO2012082741A1; US9617409B2; KR20140045305A; EP2652048B1; KR101821846B1; US20130289137A1; JP5964856B2

Abstract

The present invention describes methods for preparing a pigment particle dispersion. Specifically, a premix composition including pigments, dispersants and a liquid carrier is milled by a solid milling agent to predetermined particle size. The solid milling agent is solubilized in the liquid carrier which eliminates the need for separating the solid milling agent from the dispersion.

Description

The method of solubilising grinding medium in the pigment particles dispersion liquid

The present invention requires to submit on December 13rd, 2010, sequence number is 61/422,368, denomination of invention is the right of priority of the U.S. Provisional Application of " MILLING MEDIA RENDERED SOLUBLE AFTER COMPLETION OF DISPERSION ".In situation about allowing, by being incorporated herein with reference to the theme integral body with this application.

Technical field

The invention describes the method for using the solid abrasive agent to prepare the pigment particles dispersion liquid, described solid abrasive agent after obtaining predetermined particle size in dispersion liquid by solubilising.The present invention has also described the method for preparing the pigment particles dispersion liquid, and the method does not need separate solid abrasive from dispersion liquid after obtaining predetermined granularity.

Background technology

Grinding technics is known and has used centuries in the various application that include but not limited to the typography, medicine and food.Grinding is usually directed to utilize grinding medium to carry out the random collision of repetition to being suspended in solids in slurry or the suspension within cycle predetermined time by impact, shearing and cavitation force.By doing like this, particle failure or depolymerize to little and uniform granularity and/or size-grade distribution.

Select suitable grinding medium type and shape according to the application of dispersion liquid and granularity and/or the size-grade distribution of expectation.Typical grinding medium comprises ceramic bead, granulated glass sphere, stainless shot and solid polymer resin pearl.The pollutent that polymeric media can be used for reducing or prevents from can existing when the grinding medium that uses other type such as pottery or metal medium.

The efficient that the predetermined particle size of the granularity of reduction dispersion liquid and/or acquisition dispersion liquid distributes also depends on the size of grinding medium.About 0.2mm needing to can be used for the application that more needs of the dispersion of small grain size and better quality to the less grinding medium of about 0.65mm scope, for example can be used for jetted ink or high glossiness and packs in the printing ink.In addition, for the wide range product that includes but not limited to carbon black and pigment dyestuff, grinding medium can help the mean particle size of dispersion liquid is reduced to less than 100nm less than about 0.1mm.

Usually, at industrial use recirculation shredder, as derive from the recirculation shredder of Eiger, Drais or Netzsch, perhaps discrete levelling machine (discrete pass mill), as the discrete levelling machine that derives from Buhler, Premier or Dyno grinds.In case obtain the predetermined particle size of dispersion liquid, then grinding stops.Usually, use sieve or gap that grinding medium is retained in the shredder.Another kind of means are after obtaining predetermined particle size, in mixing tank dispersion liquid are mixed with grinding medium, and grinding medium filtered from dispersion liquid or separate.Filter or separate and reduced turnout needed extra time.In addition, because between filtration or separation period, can not from dispersion liquid, separate all grinding mediums, so the finished product comprise pollutent inevitably.When adopting pottery or metal as grinding medium, this especially counts for much.

Therefore, in the art need to be for the manufacture of effective grinding technics of the pigment particles dispersion liquid of predetermined particle size.Also need to be for the manufacture of the more not expensive technique of the pigment particles dispersion liquid of predetermined particle size.In addition, also need in the art to be substantially free of the pigment particles dispersion liquid of the predetermined particle size of pollutent.

Summary of the invention

An object of the present invention is to provide a kind of effective grinding technics, it is by improving turnout make paints predetermined particle size and/or the size-grade distribution of particle dispersion.

Another object of the present invention provides a kind of more not expensive grinding technics, and it is for the manufacture of submicron particle size and/or the size-grade distribution of pigment particles dispersion liquid.

Another purpose of the present invention provides a kind of method, and it is for the manufacture of the predetermined particle size that is substantially free of pollutent and/or size-grade distribution.

A further object of the present invention provides predetermined particle size and/or the size-grade distribution that is substantially free of pollutent.

The invention describes a kind of novel method, it is for the preparation of the original position dispersible pigment dispersion of predetermined particle size.The invention provides a kind of premix compositions that comprises one or more pigment, one or more dispersion agents and liquid vehicle.In the presence of the solid abrasive agent that substantially is insoluble to liquid vehicle, this premix compositions is ground to predetermined particle size.Further step is included in the liquid vehicle solid abrasive agent solubilising.

In an exemplary embodiment, after the predetermined particle size that obtains premix compositions, with solid abrasive agent solubilising.In another exemplary embodiment also, by via in the pH regulator and the solid abrasive agent implement step with solid abrasive agent solubilising.In the exemplary embodiment that substitutes, by the step of following enforcement with solid abrasive agent solubilising: in premix compositions, add one or more added solvent, thereby so that the solid abrasive agent dissolve in the liquid vehicle composition of premix compositions.

It will be apparent to those skilled in the art that can modifications and variations of the present invention are in the situation that does not deviate from the subject or scope of the present invention.Therefore, be intended that, the modifications and variations of the present invention that provide are provided in the present invention, as long as they are in the scope of appended claims book and its equivalent.

Embodiment

A. definition

B. the method for preparing the pigment particles dispersion liquid

1. premix compositions

A. particle

B. liquid vehicle

C. dispersion agent

D. supplementary component

2. in the presence of grinding medium, grind premix compositions

A. grinding medium

B. particle dispersion

3. solubilising grinding medium

A.pH regulates

B. add one or more solvents

C.pH regulates the interpolation with one or more solvents

4. exemplary methods

C. embodiment

A. definition

The technology that this paper provides and the definition of scientific terminology comprise at that time desired definition.These definition also do not mean that it is restrictive, because to described definition the other side of not enumerating can be arranged, such as the common aspect of understanding of those skilled in the art of the invention.Except as otherwise noted, otherwise all patents, patent application, the application of having announced and the publication that will in whole disclosures of this paper, relate to by reference, website and other open material all be incorporated herein.If there are a plurality of definition in term herein, then be as the criterion with the definition in this section.In the situation of quoting network address (URL) or other this sign or address, should understand, this sign can change and the internet on customizing messages can come and go, but equal information is known and can be such as easily obtaining by searching for Internet and/or suitable database.It is quoted availability and the public dissemination that has proved this information.

Should be understood that above-mentioned general description and following detailed description all only are exemplary and illustrative, and do not have restricted to claimed theme.In this application, unless specify in addition, the use of singulative comprises the plural number of referent.In this application, except as otherwise noted, otherwise use "or" refer to " and/or ".In addition, " to comprise " be not restrictive to term.

Scope used herein and amount can be expressed as " pact " special value or scope." pact " also comprises accurate amount.Therefore, " about 10% " refers to " about 10% " and " 10% ".

" optional " used herein or " randomly " refer to that event or the situation described subsequently occur or do not occur, and described description comprise example that event or situation occur with and the example that do not occur.For example, the optional group that replaces refers to that this group is unsubstituted or replaces.

Singulative used herein comprises the plural number of referent, unless show clearly in content and be not like this.Therefore, the composition that for example, comprises " solvent " comprises the composition with one or more solvents.

" combination " used herein refer to two or multinomial between any associating.This associating can be the space, perhaps refers to use two or multinomial for common purpose.

" composition " used herein refers to any mixture of two or more products or compound (such as solvent, resin, additive etc.).It can be solution, suspension, liquid, powder, paste, water-based or non-aqueous preparation or their arbitrary combination.

" homogeneous " about composition used herein refers to composition as mixture, comprises as solution or suspension being in the liquid phase.

Term used herein " grinding " refer to for stir, grind, fragmentation, pulverizing, compression, roll-in, perhaps otherwise reduce the technique of the size of particle.This grinding can for example be reduced to pigment particles powder or small-particle.

B. the method for preparing the dispersion liquid of pigment particles

The invention provides a kind of method for preparing original position pigment particles dispersion liquid.Described method is used solid abrasive agent such as caustic solubility, solubility in acid or solvent soluble fluoropolymer resin, and it finishes (being that granularity reduces) at grinding technics afterwards can be by solubilising in dispersion liquid.In addition, in case finish particle dispersion, then method provided by the invention does not need independent step that grinding medium is separated or filters from dispersion liquid.Especially, method provided by the invention can be used for preparing the pigment particles dispersion liquid.Because these features are compared with art methods existing, that use the insoluble abrasive that need to separate from dispersion liquid after grinding to prepare the pigment particles dispersion liquid, described method is more favourable.

In an exemplary embodiment, the method comprises: the premix compositions for preparing one or more particles, one or more liquid vehicles, one or more dispersion agents and optional one or more additives; In the presence of the solid abrasive agent that substantially is insoluble to liquid vehicle, premix compositions is stirred; And obtaining after predetermined particle size descends, in liquid vehicle with solid abrasive agent solubilising.

In an exemplary embodiment, the method comprises solid abrasive agent such as caustic solubility, solubility in acid or solvent soluble fluoropolymer resin, and it can be as grinding medium in the presence of the premix compositions of particle, dispersion agent, liquid vehicle and optional other additive.The solid abrasive agent is insoluble to liquid vehicle substantially.Premixture and solid abrasive agent are ground, descend until enough granularities occur.In another exemplary embodiment, implement to grind by stirring.In case the pigment particles of premixture is dispersed (namely finishing granularity descends), then can make the solid abrasive agent become the part of pigment particles dispersion liquid by character and the agent of solubilising solid abrasive that changes liquid vehicle.In an exemplary embodiment, can pass through pH regulator, for example change the character of liquid vehicle by adding alkali or acid.In another exemplary embodiment, can be by adding one or more solvents if the solvent of dissolving abrasive changes the character of liquid vehicle.In going back another exemplary embodiment, can change by pH regulator and the combination of adding one or more solvents the character of liquid vehicle.In method provided by the invention, become the composition of pigment particles dispersion liquid by the resin of solubilising (being dispersed).

In an exemplary embodiment of method provided by the invention, select to be used for the basic undissolved solid abrasive of liquid vehicle of premix compositions.In an exemplary embodiment, the method can be carried out in water-based system.Water-based system can be water for example.Perhaps, water-based system can be the mixture of the water mutual solubility solvent of water and basic undissolved solid abrasive.In an exemplary embodiment, the method can be carried out in based on the system of organic solvent.

The explanation of the composition of the step of the method and the method is provided in the segmentation of back.

1. premix compositions

Method provided by the invention comprises the premix compositions for preparing one or more particles, one or more liquid vehicles and one or more dispersion agents.In some embodiments, this premix compositions can comprise one or more additives.

A. particle

The premix compositions that uses in the method provided by the invention can comprise can be in medium grinder polished Arbitrary Particles such as any crystallization or unbodied solid material.Polished particle for example can comprise: drug material, food, pigment, industrial coating and makeup.Usually, compound is to be the solid of the mixture of monocrystalline formula, crystallized form, amorphous solid, the perhaps mixture of polished solid.Comprise some unusual size ranges of small-particle that can form dispersion liquid in liquid vehicle (solvent) although compound can comprise, the size of at least a portion composition of solid is usually greater than the size of the very small-particle of making among the present invention.This particle can be organic solid, crystallization or unbodied material, and perhaps they can be inoganic solids, as long as can their size be descended by grinding technics.Organic solid can be single compound or the mixture of the independent crystallized form of compound, enantiomer, optical isomer, racemic mixture, diastereomer, constitutional isomer, blend, glass, one matter, perhaps can comprise preparation such as pigment colorant and the surfactant of a lot of polymorphic forms, eutectic mixture or different compounds.This particle for example can be: the solid of precipitation, the solid of recrystallization, the solid that part is ground is such as the solid of medium milling in advance, the solid of jet grinding, the solid that part grinds, micronized solid, the solid of pulverizing, the solid that ball grinds, the solid that grinds, the solid of distillation, evaporation residue, be derived from the solid of synthesis technique, by from mixture such as reaction product or plant or tissue extract, extracting such as organic solvent extraction or supercritical fluid extraction and the solid that obtains.Usually, when water was liquid vehicle or solvent, this solid was substantially water insoluble or fully water insoluble.

The example of the solid material that can grind according to method provided by the invention comprises: the solid tinting material is such as the pigment of the printing-ink that is used for ink jet printing or conventional printing; The plastics tinting material; Electronical display color filter array high-clarity tinting material; Solid sensitive materials such as dyestuff; Solid cosmetic composition; The solid car paint; Solid paint for building construction; The solid state chemistry product; The solid metal powder; Solid catalytic material; Catalyzer solid supported material; Can be used for analyzing stationary solid phase particle or support materials with preparative chromatography; Can be used for comprising solid toner materials such as black toner material and the color toner material of printing application and the xeroprinting of laser printing; And solid pharmaceutical reagent, comprise water soluble, treatment water insoluble, basically water insoluble and poorly water-soluble and diagnosing developing agent, medical active agent, medicament, plant and herbal extract, medicine, prodrug, pharmaceutical preparation, diagnosing developing agent etc.

In method provided by the invention, use pigment can comprise any pigment.Pigment can be the form of organic or inorganic pigment, and can comprise special pigment.The example of pigment includes but not limited to: carbon black, phthalocyanine (for example, phthalocyanine blue and phthalocyanine green), quinacridone (pinkish red such as quinacridone), perylene, purple cyclic ketones, diketone pyrroles, pyrroles, thioindigo, anthraquinone, indanthrene, anthracene pyrimidine, flavanthrone, pyranthrone, anthanthrone, two Piperazine, triaryl carbon And quinophthalone; The dianisidine orange; Dinitro aniline orange; Carbazole violet; Azo-compound (for example azophloxine and azophosphine); Dyestuff and the pigment that in international colour index (Colour Index International), finds, perhaps their arbitrary combination of precipitation.Method provided by the invention can be used for disperseing the combination of single pigment or pigment or comprises pigment and the combination of dye class material.

In some embodiments, one or more of pigment can be phthalocyanine (PCN) indigo plant.In some instances, can be to the crystal modifier of interpolation PCN indigo plant in the premix compositions.The crystal modifier of PCN indigo plant includes but not limited to: alkyl pyrrolidone, glycol, dibasic ester and amine.In other example, can add the noncrystalline and non-coagulation additives of PCN indigo plant or synergistic agent in the premix compositions with the stability of raising composition.Suitable additive comprises but is not limited to: phthaloyl imino methylene radical phthalocyanine (Pc); Naphthalimido methylene radical Pc; Pc sulfonic acid and primary amine, secondary amine, tertiary amine and quaternary ammonium are or/and the salt of ether amine; Pc and primary amine, secondary amine, diamines, the sulphonamide of polyamines or ether amine is such as poly-alkoxy C uPc sulphonamide; The acid amides of Pc carboxylic acid; And the alkyl Pc of straight chain and side chain or alkanol Pc.The premix compositions of method provided by the invention can comprise one or more crystal modifiers or one or more additives of PCN indigo plant, perhaps their combination.

In the premix compositions that in method provided by the invention, uses, in the per-cent (%) (% by weight) with respect to the weight of composition, for example, the total amount of tinting material can for or be about 5% to 80%, such as: 5% to 10%, 5% to 15%, 5% to 25%, 5% to 30%, 5% to 40%, 5% to 50%, 5% to 60%, 5% to 70%, 5% to 80%, 10% to 20%, 10% to 30%, 10% to 40%, 10% to 50%, 10% to 60%, 10% to 70%, 10% to 80%, 15% to 25%, 15% to 30%, 15% to 35%, 15% to 40%, 15% to 45%, 15% to 50%, 15% to 60%, 15% to 70%, 15% to 80%, 20% to 30%, 20% to 40%, 20% to 50%, 20% to 60%, 20% to 70%, 20% to 80%, 25% to 30%, 25% to 35%, 25% to 40%, 25% to 45%, 25% to 50%, 25% to 60%, 25% to 70%, 25% to 75%, 25% to 80%, 30% to 40%, 30% to 50%, 30% to 60%, 30% to 70%, 30% to 75%, 40% to 50%, 40% to 55%, 40% to 60%, 40% to 65%, 40% to 70%, 40% to 75%, 40% to 80%, 45% to 50%, 45% to 55%, 45% to 60%, 45% to 65%, 45% to 70%, 45% to 75%, 45% to 80%, 50% to 55%, 50% to 60%, 50% to 65%, 50% to 70%, 50% to 75%, 50% to 80%, 55% to 60%, 55% to 65%, 55% to 70%, 55% to 75%, 60% to 70% and 60% to 80%.

Usually, composition comprises the tinting material less than 80% (% by weight).For example, composition provided by the invention comprise at least or at least about: 5%, 7%, 10%, 12%, 15%, 17%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 30%, 35%, 40%, 42%, 45%, 48%, 50%, 55%, 60%, 65%, 70%, 75%, but less than 80% all coloring agent.

B. liquid vehicle

The premix compositions that uses in the method provided by the invention comprises one or more liquid vehicles or solvent.In grinding technics, bring into use liquid vehicle to make particle suspension and make its dispersion by grinding or stirring.Character based on one or more expectations is selected liquid vehicle as substantially not dissolving grinding medium.

In method provided by the invention, select to be used for the basic undissolved solid abrasive of liquid vehicle of premix compositions.Method provided by the invention can be carried out in water-based system.Water-based system can be water for example.Perhaps, water-based system can be the mixture of the water mutual solubility solvent of water and basic undissolved solid abrasive.This water mutual solubility solvent can be acetone.Perhaps, water mutual solubility solvent can be acetonitrile.In another embodiment, water mutual solubility solvent can be tetrahydrofuran (THF).In going back an embodiment, water mutual solubility solvent is alcohol.In another embodiment, water mutual solubility solvent can be acetone, acetonitrile, the mixture of tetrahydrofuran (THF) or alcohol.

Method provided by the invention can be carried out in based on the system of organic solvent.System based on organic solvent can be the solvent of basic undissolved solid abrasive.For example, the system based on organic solvent can be glycol ethers, glycol ethers acetic ester, alkyl acetate, ketone, pimelinketone, alcohol, aromatic hydrocarbon, aliphatic hydrocrbon, ether, ester, perhaps their mixture.This organic solvent can be alcohol.Perhaps, organic solvent can be pimelinketone.In another embodiment, organic solvent can be the mixture of glycol ethers, glycol ethers acetic ester, alkyl acetate, ketone, pimelinketone, alcohol, aromatic hydrocarbon, aliphatic hydrocrbon, ether or ester.

Suitable liquid vehicle comprises water or non-aqueous solvent, such as, aliphatic hydrocrbon such as heptane, hexane and pentane; The cyclic hydrocarbon of cyclic hydrocarbon such as pimelinketone and replacement such as ethylcyclohexane; Ketone; Ether; Ester; Petroleum distillate such as petroleum naphtha, sherwood oil and light aliphatic solvents; Aromatic hydrocarbon and compound such as dimethylbenzene and toluene; Alkyl acetate such as ethyl acetate, isopropyl acetate, butylacetate, propylene glycol methyl ether acetate (PM acetic ester) and n-propyl acetate; Two pure and mild glycol ethers such as MPG, dipropylene glycol, 1-oxyethyl group-2-propyl alcohol, 1-propoxy--propyl alcohol (PROPOSOL solvent P), propylene glycol positive propyl ether, n-butyl ether, diethylene glycol monobutyl ether, methyl proxitol and Pyranton; The glycol ethers acetic ester; And alcohol is such as butanols, 3-methoxyl group-butanols, ethanol, propyl alcohol, Virahol and n-propyl alcohol.In the premix compositions that uses in method provided by the invention, liquid vehicle can be the single liquid carrier or can be the mixture of one or more liquid vehicles.

In some embodiments, when by pH regulator in final particle dispersion during with the grinding medium solubilising, liquid vehicle can be water.In other embodiments, when by pH regulator during with the grinding medium solubilising, liquid vehicle can be the combination of liquid vehicle such as water and the water mutual solubility solvent that does not substantially dissolve grinding medium.In exemplary methods, when by pH regulator during with the grinding medium solubilising, liquid vehicle is water.

In some embodiments, when by adding one or more solvents in final particle dispersion during with the grinding medium solubilising, the liquid vehicle in the premix compositions can be organic solvent.In other embodiments, described liquid vehicle can be the mixture of one or more liquid vehicles.In an exemplary embodiment, when by adding one or more solvents in final particle dispersion during with the dispersion medium solubilising, the liquid vehicle in the premix compositions can be alcohol.

C. dispersion agent

The premix compositions that uses in the method provided by the invention comprises one or more dispersion agents.Dispersion agent is generally used for the pigment particles in solvent stability or the liquid vehicle.Dispersion agent also is generally used for improving the separation of particle and prevents particle precipitation or caking.Select dispersion agent based on the solvent system of using in one or more Considerations such as the premix compositions and particle.

Suitable dispersion agent comprises natural or synthetic dispersing agent such as tensio-active agent, resin, polymkeric substance, or their mixture.Tensio-active agent can comprise synthetic surfactant such as anion surfactant, nonionogenic tenside, cats product and amphoterics, or natural surface active agent.Anion surfactant can include but not limited to: phosphoric acid ester, carboxylic-acid, sulfonate (ester) and vitriol (ester).Nonionogenic tenside can include but not limited to: alkynes class tensio-active agent (acetylenics), alkylphenol ethoxylate/propoxylated glycerine, Pluronic PE 6800, the alcohol ethoxylate of straight or branched and ester.Cats product can be selected from primary amine, secondary amine, tertiary amine and quaternary ammonium and imide.Suitable amphoterics for example can comprise: the derivative of aliphatic secondary amine and tertiary amine; An alkali metal salt, alkaline earth salt, ammonium salt or the substituted ammonium salt of both sexes carboxyl glycine alkyl ester and both sexes carboxyl alkyl propionates; Both sexes dipropionic acid alkyl ester, both sexes oxalic acid alkyl ester, both sexes glycine alkyl ester and both sexes alkyl propionates; Imino-alkyl propionates, imino-diacetic alkyl propionates and both sexes propyl sulfonic acid alkyl ester.Natural surface active agent can include but not limited to: Yelkin TTS, lipid acid, glucamide, glyceryl ester and polysaccharide.Exemplary surfactants comprises octylphenol ethoxylate and alkynes class tensio-active agent, and the tensio-active agent that finds in McCutcheon tensio-active agent and emulsifying agent catalogue (McCutcheon ' s Directory of Surfactants and Emulsifiers).

Make resin or polymkeric substance effective in dispersed color, it is dissolved in solvent or the liquid vehicle.The resin that uses in the premix compositions of method provided by the invention or polymkeric substance can comprise resin or the polymkeric substance with acid or alkali functionality, it is neutralized or dissolves, thereby so that its dissolve in the solvent or liquid vehicle that uses in the premix compositions.For example, have that the resin of acid or alkali functionality or polymkeric substance can be neutralized and so that water soluble.Described resin or polymkeric substance can comprise resin or the polymkeric substance with acid or alkali functionality, and it can directly be dissolved in the solvent or liquid vehicle that uses in the premix compositions.For example, the resin or the polymkeric substance that do not have acid or an alkali functionality can directly be dissolved in the organic solvent.

Suitable resin or polymkeric substance can comprise resin or polymkeric substance such as acrylic resin or the polymkeric substance with sour functionality, and can include but not limited to: acrylate resin, methacrylate resin, methyl-methacrylate resin, cinnamic acrylic ester, phenylethylene-maleic anhydride and other multipolymer well known by persons skilled in the art.Suitable resin or polymkeric substance can comprise resin cation (R.C.) such as acid imide resin and other resin cation (R.C.) well known by persons skilled in the art.Operable resin or polymkeric substance include but not limited in organic solvent or carrier: acrylate resin, urea formaldehyde, vinyl-based resin, ketone resin and Resins, epoxy.

In the particular exemplary embodiment, resin or polymkeric substance can neutralize with alkali, and described alkali is such as ammonia; Amine such as mono aminoethane (MEA) and triethylamine (TEA); Amino-2-methyl-1-propyl alcohol such as AMP ^TM95 (Dow); Oxyhydroxide such as sodium hydroxide and potassium hydroxide; And arbitrarily other alkali well known by persons skilled in the art.In other embodiments, resin or polymkeric substance can neutralize with acid, and described acid is such as lactic acid or acetic acid or arbitrarily other acid well known by persons skilled in the art.

Also have a lot of commercially available dispersion agents, it includes but not limited to

(Rhodia (Rhodia)),

(the Dow Chemical Company (Dow)),

(Rhodia),

(Rhodia),

(vapour Bagong department (Ciba)),

(Lubrizol Corp. (Lubrizol)),

(Bi Ke chemical company (BYK Chemie)),

(Di Gao company (Tego)),

(BASF AG (BASF)),

(DSM company (DSM)),

(the special company (Cytec) of cyanogen),

(the Dow Chemical Company),

(Cray Valleylad Inc. (Cray Valley)) and (the Dow Chemical Company), (Wa Ke company (Wacker)) and other dispersion agents well known by persons skilled in the art.

In the premix compositions that in method provided by the invention, uses, can use a kind of or more than a kind of dispersion agent.In the premix compositions that in method provided by the invention, uses, can use one or more tensio-active agents, resin or polymkeric substance or their combination.

In composition provided by the invention, in the per-cent (%) (% by weight) with respect to the weight of premix compositions, for example, the total amount of dispersion agent can for or be about composition weight 1% to 25%, such as 1% to 5%, 1% to 10%, 1% to 15%, 1% to 20%, 1% to 25%, 5% to 10%, 5% to 15%, 5% to 20%, 5% to 25%, 10% to 15%, 10% to 20%, 10% to 25%, 15% to 20%, 15% to 25% and 20% to 25%.Usually, premixed mixture comprises the dispersion agent less than 25 % by weight.For example, the premixed mixture of using in the method provided by the invention comprise at least or at least about: 1%, 3%, 5%, 7%, 10%, 12%, 15%, 17%, 19%, 20%, 21%, 22%, 23%, 24%, but less than whole dispersion agents of 25% (% by weight).

D. supplementary component

The premix compositions that uses in the method provided by the invention optionally comprises any of composition such as sterilant, defoamer, wetting agent, flowing agent and levelling agent, perhaps their combination.Select supplementary component based on the character of premix compositions and pigment particles dispersion liquid such as solvent system and particle types.

Usually to such as adding sterilant in the composition of inkjet ink composition to suppress microorganism in the printing ink such as the growth of mould and fungi.The example of suitable sterilant includes but not limited to: Sodium dehydroacetate, 2-phenoxyethyl alcohol, Sodium Benzoate, pyrithione-1-sodium oxide, ethyl p-hydroxybenzoate and BIT and their salt.Exemplary commercially available sterilant is PROXEL ^TMSterilant (Aoqi Chemical Co., Ltd (Arch Chemicals)).

Can be to wherein adding defoamer to prevent the foaming of composition during the preparation of premix compositions.Can use the known any appropriate defoamer of persons skilled in the art, the defoamer that preferably can dissolve each other with liquid.Suitable defoamer includes but not limited to: polysiloxane defoamers and alkynes defoamer.In some embodiments, defoamer can contain dipropylene glycol and 2,5,8,11-tetramethyl--6-dodecylene-5,8-glycol.Exemplary commercially available defoamer is Surfynol DF-110D (air products company (Air Products)).

Can also use wetting agent, it includes but not limited to: glycol comprises propylene glycol, polypropylene glycol, ethylene glycol, polyoxyethylene glycol, Diethylene Glycol, TEG; Sorbitol Powder, glycerine, triacetin, METHYLPYRROLIDONE, glycerine, urea, thiocarbamide, ethylidene-urea, alkyl urea, alkyl thiourea, dialkyl ureas and dialkyl thiourea; Glycol comprises ethylene glycol, propylene glycol, glycerol, butyleneglycol, pentanediol and hexylene glycol; And their mixture and derivative.

2. in the presence of grinding medium, grind premixed mixture

In method provided by the invention, in the presence of the insoluble solid grinding medium that substantially is insoluble to liquid vehicle, preferably by stirring the particle in the premix compositions is ground.In method provided by the invention, can select grinding medium, so that in a single day occuring, enough granularities descend, then it dissolves in solvent or the liquid vehicle of premix compositions.Can also select grinding medium, so that the pigment particles dispersion liquid can tolerate the existence of the resin of dispersion.Usually fluoropolymer resin such as sour functionality styrene-acrylonitrile copolymer acid resin are used for dispersion liquid and printing-ink.They can be provided as the value of dispersion agent and damping of shocks agent, and they are so that can again be dissolved in the printing-ink and improvement flowing from the flexible printing machine anilox roll.

A. grinding medium

Grinding medium can be solid, noncrosslinking fluoropolymer resin, and it is insoluble to the liquid vehicle of selecting to be used for premix compositions substantially.After granularity decline is finished, can be with the polymeric grinding media solubilising that uses in the method provided by the invention in liquid vehicle.If the mechanism of solubilising is pH regulator, then polymeric grinding media can comprise the functionality for neutralization.For example, polymeric grinding media can comprise acid functional or alkaline functionality.If the mechanism of solubilising is for adding one or more solvents, then polymeric grinding media can comprise so that grinding medium dissolves in the functional group of organic solvent.

The polymeric grinding media of using in the method provided by the invention is insoluble in the liquid vehicle, and can be by solubilising after granularity decline is finished.The suitable polymeric grinding media that can use in method provided by the invention comprises non-crosslinked resin, such as cinnamic acrylic ester, imide and vinylchlorid/vinyl acetate polymer resin.

Spendable exemplary solid polymer resin can include but not limited in the method provided by the invention: acrylic resin such as styrene-propene acid resin; phenoxy resin; ketone resin; urea formaldehyde; Resins, epoxy; vinyl chloride resin; vinylchlorid/vinyl acetate resin; rhodia resin (such as cellulose acetate butyrate); vibrin; acrylate resin; methacrylate resin; styrol copolymer; polyacrylic ester such as polymethylmethacrylate; polycarbonate, polyacetal, vinyl chloride-base polymer and multipolymer; urethane; polymeric amide, tetrafluoroethylene and other fluoropolymer, high density polyethylene(HDPE); polypropylene; ether of cellulose and ester such as rhodia, poly-hydroxyl-metacrylate, Poly(Hydroxyethyl Methacrylate); the polymkeric substance of silicone-containing such as polysiloxane; biodegradable polymkeric substance such as polylactide; PGA; the multipolymer of rac-Lactide and glycollide, polyanhydride, poly hydroxy ethyl acrylate; poly-iminocarbonic ester; poly-N-acyl group oxyproline ester, poly-N-palmitoyl oxyproline ester, vinyl-vinyl acetate copolymer; poe; polycaprolactone, polyphosphonitrile, and the solid polymer resin of the above-mentioned type of any modification.These resins can be used alone or in combination use of two or more.

Solid polymer resin can be with the functionalized resin of one or more acidic-groups.Exemplary acidic functionality includes but not limited to: carboxyl, phosphate-based, and other acidic-group well known by persons skilled in the art.In some embodiments, the acid number of solid polymer resin can be equal to or higher than 200, such as for example being equal to or higher than 215,220,225,230,240,250 or higher.In other embodiments, the acid number of solid polymer resin can be equal to or higher than 100, such as for example being equal to or higher than 105,110,115,125,135,145,150 or higher.

Solid polymer resin can be with the functionalized resin of one or more basic groups.Exemplary basic functionality includes but not limited to amino, and other basic group well known by persons skilled in the art.

In method provided by the invention, grinding medium can be 20:1 to 1:20 by volume to the ratio of pigment.In some embodiments, grinding medium to the ratio of pigment for or be about: 20:1,19:1,18:1,17:1,16:1,15:1,14:1,13:1,12:1,11:1,10:1,9:1,8:1,7:1,6:1,5:1,4:1,3:1,2:1 or 1:1 or less.In other embodiments, pigment to the ratio of grinding medium for or be about: 20:1,19:1,18:1,17:1,16:1,15:1,14:1,13:1,12:1,11:1,10:1,9:1,8:1,7:1,6:1,5:1,4:1,3:1,2:1 or 1:1 or less.

The exemplary solid polymer resin that uses in the method provided by the invention comprises for example cinnamic acrylic ester fluoropolymer resin.Also have many commercially available cinnamic acrylic ester fluoropolymer resins, it includes but not limited to: derive from BASF AG

HPD-96,580,586,611,633,674,678,682 and 690.

Spendable another exemplary solid polymer resin comprises for example vinylchlorid/vinyl acetate polymer resin in method provided by the invention.Exemplary commercially available vinylchlorid/vinyl acetate polymer resin comprises the Vinnol H15/50 that derives from Wa Ke company.

The acid imide resin is the example of spendable solid polymer resin in method provided by the invention.Exemplary commercially available acid imide fluoropolymer resin comprises the SMA1000I that derives from Cray Valleylad Inc..

Usually provide the dissolving grade resin bead with the bead form.Can in premix compositions, add resin with the bead form, perhaps can before being used for the premix compositions of method provided by the invention, resin be pulverized.Can be by any means well known by persons skilled in the art such as sledge mill, in liquid vehicle, stirring under the shearing condition or bead oersted (osterizing) (namely grinding in oersted (Oster) blender) pulverized resin.Oerstedization can obtain being of a size of about 0.25 micron extremely about 87.5 microns fluoropolymer resin particle (new handkerchief Tyke (Sympatec) laser diffraction, utilize to do, carry out through the material of oersted), wherein 90% particle is of a size of about 0.35 micron to about 6.38 microns.

B. form dispersion liquid

In method provided by the invention, premix compositions and grinding medium ground be in the same place.Can utilize blade, rotor stator or arbitrarily other suitable mixing or milling apparatus, under high-speed stirring, in tank, grind.Milling apparatus can be the simple receptacle with super mixer, perhaps any conventional is ground design, comprises ball mill, agitating ball mill, sand mill, pebble mill, horizontal medium grinder, vertical medium grinder, air spray shredder, roller mill, runner milling, oscillating mill, planetary mills or ball mill.Also can be together with high speed disperser such as Ke Lesi company (Cowles) decollator, rotor-stator mixing tank, maybe can provide other conventional stirrers of high fluid velocity and high-shear to grind.Mixing tank can include but not limited to: Sawtooth blade, Ke Lesi blade, homogenizer, Silverson mixing tank, D blade (D-Blade), rotor stator or water screw.

In exemplary embodiment, can implement to stir, until enough granularity decline occurs and form the dispersion liquid with predetermined particle size.Mixing time is generally 5 minutes or about 5 minutes to 40 hours or about 40 hours, but according to particle types and mass parameter, other mixing time also is feasible.Usually, mixing time is so that the granularity that realizes expecting descends, such as the time of for example submicron particle size.In method provided by the invention, mixing time can be about 1 hour to about 20 hours.

3. with the grinding medium solubilising

In exemplary embodiment, after obtaining the predetermined particle size of premix compositions, in liquid vehicle with solid abrasive agent solubilising.Character that can be by changing liquid vehicle is as implementing solubilising by pH regulator.Perhaps, can implement solubilising by in premix compositions, adding one or more solvents.The selection of solubilising technology is based on the dissolution characteristics of polymeric grinding media.

In exemplary methods provided by the invention, after granularity decline is finished and is dispersed in pigment particles in the composition, can be with solid polymer abrasive solubilising in premix compositions.Can select the solid polymer abrasive, so that it is insoluble in the liquid vehicle that exists in the premix compositions substantially, still can pass through to change character solubilising in liquid vehicle of solvent system.

A.pH regulates

In some embodiments, can change by the pH that regulates solvent system the character of solvent system.Regulate solvent system pH can in and functional group such as acidity or basic group on the polymeric grinding media, and give the solvability of fluoropolymer resin in liquid vehicle.Polymeric grinding media becomes the part of dispersion liquid.Can regulate by for example adding acid or alkali the pH of solvent system.

In particular implementation, can in composition, add acid.Can in composition, add acid, thereby reduce the pH of composition.PH can be reduced to and make fluoropolymer resin solubilising and become the level of the part of pigment particles dispersion liquid in liquid vehicle.Can be used for regulating the pH of solvent system and the deliquescent appropriate acid of giving resin, include but not limited to: acetic acid, lactic acid, phosphoric acid, hydrochloric acid, nitric acid, perchloric acid, sulfuric acid, hydrofluoric acid, Hydrogen bromide, hydroiodic acid HI, carbonic acid, permanganic acid, chromic acid, prussic acid, nitrous acid, sulfurous acid and the well known by persons skilled in the art any acid that can be used for regulating pH.In exemplary embodiment, can realize pH regulator by adding acetic acid.

When polymeric grinding media during for solubility in acid polymeric grinding media for example, can add acid.Exemplary solubility in acid polymeric grinding media is cationoid polymerisation resin such as acid imide fluoropolymer resin.

In other embodiments, can in composition, add alkali.Can in composition, add alkali, thereby improve the pH of composition.PH can be increased to and make fluoropolymer resin solubilising and become the level of the part of pigment particles dispersion liquid in liquid vehicle.Can be used for regulating the pH of solvent system and the deliquescent appropriate base of giving resin, include but not limited to: ammonia, caustic alkali, mono aminoethane (MEA), triethylamine (TEA), amino-2-methyl-1-propyl alcohol, sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide, fluorochemical, bromide, iodide, supercarbonate, acetate, permanganate, phosphoric acid salt, chromic salt, prussiate, nitrite, sulphite, sulphite and the well known by persons skilled in the art any alkali that can be used for regulating pH.In exemplary embodiment, can realize pH regulator by adding ammonia.

When polymeric grinding media during for alkali-soluble polymer grinding medium for example, can add alkali.Exemplary solubility in acid polymeric grinding media is anionic polymeric resins such as cinnamic acrylic ester fluoropolymer resin.

In method provided by the invention, can be by realizing pH regulator with dilute solution as add acid or alkali with dilute aqueous soln.Can be with strong solution as adding acid or alkali with concentrated aqueous solutions.Can carry out the resin dissolves that realizes by pH regulator by method of adding arbitrarily acid or alkali well known by persons skilled in the art.

B. add one or more solvents

In some embodiments, can be by in composition, adding the character that one or more solvents change solution.One or more solvents that add can comprise can with the liquid vehicle compatible (dissolving each other) that uses in the premix compositions and the solvent with the dissolving power that is enough to the dissolve polymer grinding medium.Add the solvent of one or more soluble polymeric thing grinding mediums, can give the solvability of fluoropolymer resin in liquid vehicle.Therefore, polymeric grinding media becomes the part of dispersion liquid.

Can add in the composition and comprise water or non-aqueous solvent with the suitable solvent with the polymeric grinding media solubilising, such as: aliphatic hydrocrbon such as heptane, hexane and pentane; The cyclic hydrocarbon of cyclic hydrocarbon such as pimelinketone and replacement such as ethylcyclohexane; Ketone; Ether; Ester; Petroleum distillate such as petroleum naphtha, sherwood oil and light aliphatic solvents; Aromatic hydrocarbon and compound such as dimethylbenzene and toluene; Alkyl acetate such as ethyl acetate, isopropyl acetate, butylacetate, propylene glycol methyl ether acetate (PM acetic ester) and n-propyl acetate; Two pure and mild glycol ethers such as MPG, dipropylene glycol, 1-oxyethyl group-2-propyl alcohol, 1-propoxy--propyl alcohol (PROPOSOL solvent P), propylene glycol positive propyl ether, n-butyl ether, diethylene glycol monobutyl ether, methyl proxitol and Pyranton; The glycol ethers acetic ester; And alcohol is such as butanols, 3-methoxyl group-butanols, ethanol, propyl alcohol, Virahol and n-propyl alcohol.In method provided by the invention, added solvent can be single solvent or can be the mixture of one or more solvents.

Giving deliquescent exemplary methods provided by the invention to fluoropolymer resin comprises to add one or more solvents such as hydrocarbon in the premix compositions of grinding.For example, in the premix compositions through grinding, contain pure liquid vehicle such as 3-methoxyl group-butanols, add cyclic hydrocarbon such as hexanaphthene.

C.pH regulates the interpolation with one or more solvents

In some embodiments, can change by pH regulator and the combination of in the premix compositions through grinding, adding one or more solvents the character of solvent system.Can implement pH regulator and solvent adds according in the aforesaid method any.

In some embodiments of method provided by the invention, can not be separately by pH regulator or solvent add and in composition with the polymeric grinding media solubilising.For example, have low acid number such as acid number be equal to or less than 200 fluoropolymer resin can be such as by adding alkali and adding one or more solvents and realize pH regulator such as alcohol.

4. exemplary methods

Method provided by the invention comprises: the premix compositions for preparing one or more particles such as pigment, one or more liquid vehicles such as water or organic solvent, one or more dispersion agents and optional one or more additives; Substantially be insoluble to the solid abrasive agent of liquid vehicle, for example under the existence of non-cross-linked polymer resin such as alkali soluble resins, solubility in acid resin or organic solvent soluble resin, premix compositions stirred; And granularity descend finish after, such as by pH regulator, for example add acid or alkali, perhaps add one or more solvents, in liquid vehicle with solid abrasive agent solubilising.

Following method only is exemplary and the platform that can regulate is provided.Should be understood that if whole desirable propertieses of reservation method not, then can be when keeping a part of character, the step of method is changed.Can by adding or change the composition of step or each step, further change.For example, can change the enforcement order of step.

For example, exemplary methods provided by the invention can use caustic solubility negatively charged ion solid polymer resin as grinding medium such as anion styrene-acrylic polymers, and can be after particle disperses such as colo(u)rant dispersion, by pH regulator as by interpolation alkali such as ammonia with the resin solubilising.For example, can use after colo(u)rant dispersion can be by add ammonia in composition by the anion styrene-acrylic polymers of solubilising for method provided by the invention.

Use can be by the example of the method provided by the invention of the solid polymer grinding medium of solubilising in composition after granularity descends, be to use solubility in acid positively charged ion solid polymer resin such as positively charged ion acid imide polymkeric substance as the method for grinding medium, described solubility in acid positively charged ion solid polymer resin can be by pH regulator such as sour such as acetic acid and by solubilising by interpolation after particle disperses such as colo(u)rant dispersion.For example, can use after colo(u)rant dispersion can be by add acetic acid in composition by the positively charged ion acid imide polymkeric substance of solubilising for method provided by the invention.

Use can be by the example of the method provided by the invention of the solid polymer grinding medium of solubilising in composition after granularity descends, to use caustic solubility negatively charged ion solid polymer resin such as the method for low acid number anion styrene-acrylic ester polymer as grinding medium, described caustic solubility negatively charged ion solid polymer resin can be by pH regulator such as by adding alkali such as ammonia and interpolation the second solvent such as alcohol after particle disperses such as colo(u)rant dispersion, for example n-propyl alcohol and by solubilising.For example, can use after colo(u)rant dispersion can be by add ammonia and n-propyl alcohol in composition by the anion styrene-acrylic ester polymer of solubilising for method provided by the invention.

Use can be by the exemplary methods provided by the invention of the solid polymer grinding medium of solubilising in composition after granularity descends, be to use solvent soluble such as organic solvent soluble, for example 3-methoxyl group-butanols soluble solids fluoropolymer resin is as the method for grinding medium.This grinding medium includes but not limited to vinylchlorid/vinyl acetate polymer, and it can pass through interpolation the second solvent such as cyclic hydrocarbon after particle disperses such as colo(u)rant dispersion, for example pimelinketone and by solubilising.For example, method provided by the invention can be used vinylchlorid/vinyl acetate polymer, its can be by adding pimelinketone in the composition after colo(u)rant dispersion in 3-methoxyl group-butanols by solubilising.

C. embodiment

The following example of the result who comprises experiment and obtain only provides for illustrative purposes, and should be by interpretation theme required for protection.

Embodiment 1

Prepared and used the negatively charged ion solid polymer resin as a series of ink composites of grinding medium.After the granularity decline of pigment is finished (after namely stirring or grinding), by the pH with the alkali regulator solution, perhaps add the second solvent by pH regulator with in the composition, so that resin, anion styrene-acrylic resin dissolving (dispersion) are in ink composite.Utilize in addition ceramic media (0.7mm) or glass grinding media to replace dispersed negatively charged ion solid polymer resin grinding medium, prepare a series of relatively ink composites.Measure character such as colour strength, glossiness and the size-grade distribution of the ink composite that uses dispersed solid polymer grinding medium preparation, and compare with the ink composite that uses the preparation of pottery or glass grinding media.Except as otherwise noted, otherwise according to industrial standards the comparison ink composite that uses commercially available pigment is ground.

A. pass through the caustic solubility negatively charged ion solid polymer resin grinding medium of pH regulator solubilising

1. Yellow ink composition

Prepared and used caustic solubility anion styrene-acrylic acid or the like solid polymer resin as a series of Yellow ink compositions of grinding medium.By being prepared as follows Yellow ink 1-4: under Silverson mixing tank (Dong Langmeiduo (East Longmeadow), Massachusetts (MA)), combination outdoor stages Pigment Yellow 73 74 (printing ink 1-3; Production number 272-0723; Sun Chemical Corporation (Sun Chemical), Pa Xipani (Parsippany), New Jersey (NJ)) or indoor level Pigment Yellow 73 74 (printing ink 4; Production number 472-4497, sun Chemical Corporation) with Triton X-100 surfactant (the Dow Chemical Company, Midland (Midland), the state of Michigan (MI)), anion styrene-acrylic polymers

678 resin beads (acid number=215; MW=8500; BASF AG, Fu Lunhan park (Florham Park), New Jersey), DF-110D defoamer (air products company, Allentown (Allentown), Pennsylvania (PA)) and water.Printing ink 1-3 also contains Proxel sterilant (Aoqi Chemical Co., Ltd, Norwalk (Norwalk), the Connecticut State (CT)).Composition is mixed 2 hours (printing ink 1 and 4) or 4 hours (printing ink 2 and 3).Then, with the pH of ammonia neutralization solution, thereby cause

The dispersion of 678 resins in composition.Prescription is shown in the following table 1.

Prepare two kinds and also contained the resinoid relatively Yellow ink (printing ink 5 and 6) of Styrene And Chloroalkyl Acrylates.Not to use the styrene-propene acid resin as grinding medium, but before adding to it in composition, at first with ammonia it is neutralized.By being prepared as follows Yellow ink 5 and 6: under Silverson mixing tank (Dong Langmeiduo, Massachusetts), mix outdoor stages Pigment Yellow 73 74 (printing ink 5; Production number 272-0723; Sun Chemical Corporation) or indoor level Pigment Yellow 73 74 (printing ink 6; Production number 472-4497, sun Chemical Corporation), the Styrene And Chloroalkyl Acrylates base polymer that has neutralized

678 resins (printing ink 5) or

674 resins (printing ink 6; Acid number=217; MW=13000; BASF AG), DF-110D defoamer (air products company) and water.Printing ink 5 also contains Triton X-100 surfactant (the Dow Chemical Company) and Proxel sterilant (Aoqi Chemical Co., Ltd).To finish pre-mixing in 30 minutes, then at Eiger micropulverizer (Engineered Mills, Inc., Grace thunder gram (Grayslake), Illinois (IL)) upper 6 minutes (printing ink 5) or 12 minutes (printing ink 6) of ceramic media grinding that uses 0.7mm.Prescription is shown in the following table 1.

Table 1. Yellow ink composite formula

Also prepared another kind of Yellow ink composition, described Yellow ink composition also contains the styrene-propene acid resin solution of dispersion except using the styrene-acrylonitrile copolymer acid resin as the grinding medium.By being prepared as follows printing ink 7: combination 620g solids content is 59.6% C.I. pigment Yellow 14 filter cake (production number 474-4480; Sun Chemical Corporation, Pa Xipani, New Jersey) with the 124g solids content be 30%

674 resin solutions, 248g

674 grind resin beads, 2g Proxel GXL sterilant (Aoqi Chemical Co., Ltd, Norwalk, the Connecticut State), 2g DF-110D defoamer (air products company, Allentown, Pennsylvania) and 43.4g

S40/70 tensio-active agent (Rhodia).Under the Hockmeyer mixing tank, use the Ke Lesi blade with 6600RPM with composition hash total 15 hours, then by the ammonia solution that adds 95g28% it is neutralized, thereby obtains the Yellow ink composition.

With the Yellow ink of making comparisons (printing ink 8), described yellow 14 dispersion liquids are by 29.0% pigment Yellow 14,45.7% with commercially available yellow 14 dispersion liquids

674 resins (30% resin solid neutralizes with ammonia), 0.2%Proxel GXL sterilant, 0.2%DF-110D defoamer and 25.3% water form.Use the glass grinding media of 1.0mm to replace styrene-propene acids solid polymer resin grinding medium to exist

On the shredder printing ink 8 is ground.

In the priming paint (Pittsburgh (Pittsburgh), Pennsylvania) take priming paint: printing ink after the ratio of 50:1 is painted, by

Spectrophotometer (Lawrenceville (Lawrenceville), New Jersey) is measured the colour strength of printing ink 1-8.For painted, in cup, measure 50 gram white paint.Then in white paint, add 1.0 gram ink composites.Then use metallic spatula to mix, until the color even in the cup.Usually, this need to rotate about 50 scrapers that turn in about one minute to about two minutes.Then, on Leneta card (Leneta Company, Inc., not watt (Mahwah), New Jersey), ' paint down ' side by side ink composite with #30 Meyer rod, and dry with instrument air dryer.Then, to " standard " (being respectively printing ink 5-6 and 8), measure dry tone at spectrophotometer with " in batches " (printing ink 1-4 and 7).Light and reflectance curve by the spectrophotometer emission on the composition under measurement is painted (drawdown).Colour strength the comparing and measuring the reflectivity at the maximum absorption place of " standard " that be " in batches ".Compare the comparison colours intensity level that printing ink 1-4 performance is similar or higher with 6 with comparing printing ink 5.With respect to comparing printing ink 5, printing ink 1,2 and 3 obtains respectively 101.64%, 101.34% and 100.71% intensity.With respect to comparing printing ink 6, printing ink 4 shows 98.98% intensity.With respect to comparing printing ink 8, printing ink 7 shows 112% intensity.

Measure the average particle size distribution at the D50 place of each ink composite.Use Nanotrac particle-size analyzer (Mai Qike company (Microtrac), Montgomery Wei Er (Montgomeryville), Pennsylvania) to measure mean particle size.Show the result in the following table 2.

Measure the glossiness of printing ink 1-4, and compare with the gloss value that compares printing ink 5 and 6.Using 60 ° of vancometers (Bi Ke-Gartner company (BYK Gardner), Colombia (Columbia), the Maryland State (MD)) to obtain glossiness measures.

The character of table 2. Yellow ink composition

Compare with 6 with the printing ink 5 that uses the ceramic media preparation, printing ink 1-4 shows equal or higher gloss value and average size.Compare with the ink composite (printing ink 8) that uses the glass grinding media preparation, printing ink 7 can be realized less D50 average particle size distribution.These results show, can use after grinding to be prepared with respect to the printing ink that uses the preparation of pottery or glass grinding media by the anionic polymer grinding medium of solubilising, show the printing ink of equal or higher colour strength, glossiness and average granularity.

2. black ink composition

By being prepared as follows black ink composition (printing ink 9): under Silverson mixing tank (Dong Langmeiduo, Massachusetts), combination

660 Pigment blacks 7 (Cabot Co.,Ltd (Cabot Corporation), Boston (Boston), the Massachusetts) with Triton X-100 surfactant (the Dow Chemical Company, Midland, the state of Michigan), anion styrene-acrylic polymers 678 resin beads (acid number=215; MW=8500; BASF AG, Fu Lunhan park, New Jersey), DF-110D defoamer (air products company, Allentown, Pennsylvania) and water.Composition was mixed 2 hours, then use in the ammonia and pH, thereby cause

The dispersion of 678 resins in composition.Prescription is shown in the following table 3.

Prepared and also used the resinoid relatively black ink (printing ink 10) of Styrene And Chloroalkyl Acrylates.Not to use resin anion(R.A) as grinding medium, but before adding to it in composition, at first with ammonia it is neutralized.By being prepared as follows printing ink 10: under Silverson mixing tank (Dong Langmeiduo, Massachusetts), mix 660 Pigment blacks 7 (Cabot Co.,Ltd), the anion styrene-acrylic polymers that has neutralized

674 resins (acid number=217; MW=13000; BASF AG), DF-110D defoamer (air products company), Proxel sterilant (Aoqi Chemical Co., Ltd) and water.To finish pre-mixing in 30 minutes, then the ceramic dielectic at the upper 0.7mm of use of Eiger micropulverizer (Engineered Mills, Inc., Grace thunder gram, Illinois) ground 12 minutes.Prescription is shown in the following table 3.

Table 3. black ink composition prescription

According to aforesaid method, In the priming paint (Pittsburgh, Pennsylvania) take priming paint: printing ink after the ratio of 50:1 is painted, by

Spectrophotometer (Lawrenceville, New Jersey) is measured the colour strength of printing ink 9 and 10.With respect to printing ink 10, printing ink 9 shows 94.88% colour strength.Measure the glossiness of printing ink 9 and mean particle size (D50) and with relatively glossiness and the average granularity of printing ink 10 compare.Using 60 ° of vancometers (Bi Ke-Gartner company, Colombia, the Maryland State) to obtain glossiness measures.Use Nanotrac particle-size analyzer (Mai Qike company, Montgomery Wei Er, Pennsylvania) to measure mean particle size.By using #3 Meyer rod to carry out Freehandhand-drawing and utilizing Bi Ke-Gartner photodensitometer to measure, measure the optical density(OD) of printing ink 9 and 10 at uncoated Leneta paper.Show the result in the following table 4.

The character of table 4. black ink

Compare with comparing printing ink 10, printing ink 9 shows higher gloss value and average size.The optical density(OD) of printing ink 9 is suitable with printing ink 10.These results show, can use after grinding to be prepared with respect to the black ink that uses the ceramic media preparation by the anionic polymer grinding medium of solubilising, show the black ink of higher colour strength, glossiness and average granularity.

3. blue ink composition

Three kinds of blue ink compositions that prepared before using in being dispersed in composition anion styrene as grinding medium-acrylic acid or the like solid resin.By being prepared as follows printing ink 11 and 12: under Silverson mixing tank (Dong Langmeiduo, Massachusetts), combination pigment Blue 15: 3 (production number 249-9813; Sun Chemical Corporation, Pa Xipani, New Jersey) with Triton X-100 surfactant (the Dow Chemical Company, Midland, the state of Michigan), anion styrene-acrylic polymers

678 resin beads (printing ink 11; Acid number=215; MW=8500; BASF AG, Fu Lunhan park, New Jersey) or HDP-96 resin beads (printing ink 12; Acid number=220; MW=16000; BASF AG), DF-110D defoamer (air products company, Allentown, Pennsylvania) and water.Also add blue synergistic agent in printing ink 12, poly-alkoxy C uPc sulphonamide (sun Chemical Corporation) is to provide with respect to not using this synergistic agent higher stability or granularity to flocculation to increase.Composition was mixed 20 hours, then with in the ammonia with pH to cause

678 or

The dispersion of HDP-96 resin.Prescription is shown in the following table 5.

Before using in adding composition to, printing ink 13 (not shown in table) in the oersted blender, grinds the anion styrene-acrylic polymers of (oersted)

690 resin beads (acid number=240; MW=16500; BASF AG, Fu Lunhan park, New Jersey).By being prepared as follows printing ink 13: to 40.0g through oersted

Add 30.0g C.I. pigment Blue 15 in 690 resins: 3 (production number 249-1284; Sun Chemical Corporation, Pa Xipani, the New Jersey), 6.0g Zephrym SD-1121 dispersion agent (standing grain major company (Croda Inc.), Edison (Edison), the New Jersey), 0.4g DF-110D defoamer (air products company, Allentown, Pennsylvania) and the 63.6g deionized water.Under Silverson mixing tank (Dong Langmeiduo, Massachusetts), with 4400RPM composition was mixed 9 hours.

Prepared and also used the resinoid two kinds of comparison blue inks (printing ink 14 and 15) of Styrene And Chloroalkyl Acrylates.Not to use resin anion(R.A) as grinding medium, but before adding to it in composition, at first with ammonia it is neutralized.By being prepared as follows comparison printing ink 14: under Silverson mixing tank (Dong Langmeiduo, Massachusetts), hybrid pigment blue 15:3 (sun Chemical Corporation), neutralized

674 resins (acid number=217; MW=13000; BASF AG), Proxel sterilant (Aoqi Chemical Co., Ltd) and water.To finish pre-mixing in 30 minutes, then the ceramic dielectic at the upper 0.7mm of use of Eiger micropulverizer (Engineered Mills, Inc., Grace thunder gram, Illinois) ground 18 minutes.The prescription that compares printing ink 14 is shown in the following table 5.

Use material and the amount preparation identical with above-mentioned printing ink 13 to compare printing ink 15.Use ceramic media to exist Grind comparing printing ink 15 on the shredder.

Table 5. blue ink composite formula

According to aforesaid method,

In the priming paint (Pittsburgh, Pennsylvania) take priming paint: printing ink after the ratio of 50:1 is painted, by

Spectrophotometer (Lawrenceville, New Jersey) is measured the colour strength of printing ink 11-15.With respect to comparing printing ink 14, printing ink 11 and 12 shows respectively 109.18% and 102.66% colour strength.Measure the glossiness of printing ink 11 and 12 and mean particle size (D50) and with relatively glossiness and the average granularity of printing ink 14 compare.Measure the mean particle size of printing ink 13 and compare with printing ink 15 relatively.Using 60 ° of vancometers (Bi Ke-Gartner company, Colombia, the Maryland State) to obtain glossiness measures.Use Nanotrac particle-size analyzer (Mai Qike company, Montgomery Wei Er, Pennsylvania) to measure mean particle size.Show the result in the following table 6.

The character of table 6. blue ink

Compare with the comparison printing ink 14 that uses the ceramic media preparation, printing ink 11 and 12 all shows higher gloss value and can realize the dispersion liquid of less mean particle size.Compare with the comparison printing ink 15 that is prepared by identical component but use ceramic dielectic to grind, printing ink 13 also can be realized less size.The result shows, can by after grinding by the preparation of the anionic polymer grinding medium of solubilising with respect to the blue ink that uses the ceramic media preparation, show the blue ink of higher glossiness and less mean particle size.

4. purple ink composition

Two kinds of purple ink compositions that prepared before using in being dispersed in composition anion styrene as grinding medium-acrylic acid or the like solid resin.By being prepared as follows printing ink 16 and 17: combination pigment Violet 23 (production number 246-1671; Sun Chemical Corporation, Pa Xipani, New Jersey) and oersted

690 acrylic resin bead (acid number=240; MW=16500; BASF AG, Fu Lunhan park, New Jersey),

CA-887 tensio-active agent (Rhodia, new Brunswick (New Brunswick), the New Jersey), DF-110D defoamer (air products company, Allentown, Pennsylvania), Proxel GXL sterilant (Aoqi Chemical Co., Ltd, Norwalk, the Connecticut State) and water.Under Silverson mixing tank (Dong Langmeiduo, Massachusetts), with 4400RPM composition is mixed, thereby then with causing with pH in the ammonia

The dispersion of 690 resins.Prescription is shown in the following table 7.

Table 7. violet pigment dispersion composition

The third purple ink composition (printing ink 18) that has also prepared before using in being dispersed in composition anion styrene as grinding medium-acrylic acid or the like solid resin.This ink composite is except also comprising water and the resinoid slurry of styrene acrylic with the styrene-propene acid resin as the grinding medium.By under rotor stator mixers, mixing 50.6g

674 acrylic resin bead (acid number=217; MW=13,000; BASF AG) and 187.4g water with resin beads is reduced to～40 μ m prepare slurry.Then, adding 126.5g C.I. pigment Violet 23 (sun Chemical Corporation), 42.0g solids content in the slurry is 30%

674 resin solutions (BASF AG), 7.9g solids content are 40% HLD-11 dispersing additive (Keim Additec, Ji Xibeige (Kirchberg), Germany), 0.3g Proxel GXL sterilant (Aoqi Chemical Co., Ltd) and 0.3g DF-110D defoamer (air products company), and with 4400RPM with the mixing of Silverson mixing tank.Then, with the pH of ammonia neutralization solution to cause The dispersion of 674 acrylic resin beads (as grinding medium) in final distributes ink liquid.

With the comparative example of commercially available purple ink composition (printing ink 20) as printing ink 16-18.Relatively printing ink 20 also contains the styrene-propene acid resin, but with ammoniacal liquor it is neutralized before adding to it in composition.Relatively printing ink 20 contains: 38%C.I. pigment Violet 23 (production number 246-1671; Sun Chemical Corporation), 9.5% neutralized

674 resin solutions (30% resin solid) (BASF AG), 0.2%Proxel sterilant (Aoqi Chemical Co., Ltd), 0.3%DF-110D defoamer (air products company) and 52.1% water.By utilizing the 1.0mm glass grinding media to replace solid polymer resin to exist

On the shredder composition is ground.

Also prepare another kind of purple ink composition, described purple ink composition also comprises the styrene-propene acid resin solution of dispersion except using the styrene-acrylonitrile copolymer acid resin as the grinding medium.By the following printing ink 19 for preparing: combination 48.6g C.I. pigment violet 3 (production number Z99CN0904; China mountain lake pigment company), the 16.2g solids content is 30%

674 resin solutions (BASF AG), 10.0g

674 grind resin beads, 4.2g

X-100 tensio-active agent (the Dow Chemical Company), 0.3g Proxel GXL sterilant (Aoqi Chemical Co., Ltd, Norwalk, the Connecticut State), 0.3g DF-110D defoamer (air products company, Allentown, Pennsylvania) and 70.4g water.Under the Silverson mixing tank with 4400RPM with composition hash total 12 hours, then neutralize by the ammonia solution that adds 12.0g28%, thereby obtain purple ink composition (printing ink 19).

Prepared relatively purple ink (printing ink 21), described relatively purple ink (printing ink 21) uses the composition identical with printing ink 19, but with

Before 674 resins add in the composition, with ammonia this resin is neutralized.After all material all adds in the composition, use the 1.0mm glass grinding media to replace styrene-propene acids solid polymer resin grinding medium to exist On the shredder composition is ground.

Measure the average particle size distribution (printing ink 16-19) at the D50 place of each ink composite that uses styrene-propene acid resin grinding medium.Also measure the average particle size distribution (D50) (relatively printing ink 20-21) of the comparison violet pigment dispersion liquid that uses the glass grinding media grinding.Use Nanotrac particle-size analyzer (Mai Qike company, Montgomery Wei Er, Pennsylvania) to measure mean particle size.Show the result in the following table 8.

The average particle size distribution value (D50) of table 8. violet pigment dispersion liquid

Compare with comparative composition, printing ink 20, printing ink 16-18 all can realize much smaller D50 size.Printing ink 19 also can be realized frequently the D50 size less than printing ink 21.The result shows, can by being compared with the purple ink that uses glass grinding media to grind by the preparation of the grinding medium of solubilising, can realize the purple ink of less mean particle size after grinding.

According to aforesaid method, In the priming paint (Pittsburgh, Pennsylvania) take priming paint: printing ink passes through Datacolor after the ratio of 50:1 is painted Spectrophotometer (Lawrenceville, New Jersey) is measured printing ink 19 and is compared the colour strength of printing ink 21.The result shows, compares with the comparison printing ink 21 that uses the glass grinding media preparation, uses the purple ink composition (printing ink 19) of polymeric grinding media preparation can obtain 104% colour strength.

5. red ink composition

Three kinds of red ink compositions that prepared before using in being dispersed in composition anion styrene as grinding medium-acrylic acid or the like solid resin.Except using the styrene-acrylonitrile copolymer acid resin as the grinding medium, printing ink also comprises the styrene-propene acid resin solution of dispersion.By making up the following printing ink 22-24:C.I. Pigment red 57:1 (printing ink 22 and 23 for preparing; Production number 57DT819; CDR Pigments﹠amp; Dispersions, Elizabethtown (Elizabethtown), the Kentucky State (KY)) or solids content be 70.2% pigment red 4 9:2 filter cake (printing ink 24; Production number 411-4432, sun Chemical Corporation, Pa Xipani, New Jersey) with solids content be 30%

674 resin solutions (acid number=217; MW=13,000; BASF AG), 30.0

674 grind resin beads, Proxel GXL sterilant (Aoqi Chemical Co., Ltd, Norwalk, the Connecticut State), DF-110D defoamer (air products company, Allentown, Pennsylvania) and water.Under the Silverson mixing tank, with 4400RPM composition was mixed 12 hours, then neutralize by adding 28% ammonia solution, thereby obtain distributes ink liquid.Prescription is shown in the following table 9.

Prepared three kinds of relatively red inks, comparison printing ink 25-27, they use respectively the composition preparation identical with printing ink 22-24, but are inciting somebody to action

Before 674 resins add in the composition, with ammonia this resin is neutralized.After all material all adds in the composition, use the 1.0mm glass grinding media to substitute anion styrene-acrylic acid or the like solid polymer resin grinding medium,

On the shredder composition is ground.Prescription is shown in the following table 9.

Table 9. red ink composition prescription

According to aforesaid method,

In the priming paint (Pittsburgh, Pennsylvania) take priming paint: printing ink passes through Datacolor after the ratio of 50:1 is painted

Spectrophotometer (Lawrenceville, New Jersey) is measured the colour strength of printing ink 22-27.Than printing ink 25-27, red ink 22-24 shows respectively 112%, 106% and 112% colour strength with respect to red ratio relatively.These result's indications with respect to the comparison red ink composition that uses the glass grinding media preparation, use the printing ink of Styrene And Chloroalkyl Acrylates base polymer grinding medium preparation to have higher colour strength.

For the average particle size distribution of each ink composite (printing ink 22-24) that uses polymeric grinding media at several point in time measurement D50 place, and (relatively printing ink 25-27 compares respectively) with the comparison red ink composition that uses glass grinding media with it.Use Nanotrac particle-size analyzer (Mai Qike company, Montgomery Wei Er, Pennsylvania) to measure mean particle size.Result shown in the following table 10 shows, compares with the ink composite that uses the glass grinding media preparation, uses the ink composite of polymeric grinding media preparation can realize less D50 average particle size distribution.

The average particle size distribution value of table 10. red ink composition after various milling times (D50)

B. by pH regulator and the negatively charged ion solid polymer resin grinding medium that adds the second solvent solubilising

Prepared red ink composition, described red ink composition uses the negatively charged ion solid polymer resin grinding medium that dissolves in the dispersion liquid after the decline of pigment granularity is finished.Employed polymeric grinding media be can not be only by pH regulator by the low acid resin of solubilising

586 resins; Acid number=108; MW=4600).The pigment granularity descend finish after, with the combination of pH regulator and interpolation the second solvent with solid abrasive medium solubilising.

By being prepared as follows red ink 28: combination 52.5g C.I. Pigment red 57:1 (production number 57DT819; CDR) be 30% with the 17.5g solids content

674 resin solutions (acid number=217; MW=13,000; BASF AG), 14.7g

586 grind resin beads, 0.2g Proxel GXL sterilant (Aoqi Chemical Co., Ltd, Norwalk, the Connecticut State), 0.2gDF-110D defoamer (air products company, Allentown, Pennsylvania) and 64.9g water.Under Silverson mixing tank (Dong Langmeiduo, Massachusetts) with 4400RPM with composition hash total 12 hours.Then, by adding ammonia solution and the 7.5g n-propyl alcohol of 2.2g28%, will

The neutralization of 586 resins also is dispersed in the final composition.

With the red ink of making comparisons (printing ink 29), described red 57:1 dispersion liquid is by 28.7% Pigment red 57:1,36.4% with commercially available red 57:1 dispersion liquid

Resin solution (30% resin solid neutralizes with ammonia), 0.2%Proxel GXL sterilant, 0.2%DF-110D defoamer and 34.5% water form.Use the glass grinding media of 1.0mm to replace styrene-acrylonitrile copolymer acids solid polymer resin grinding medium to exist

Grind comparing printing ink 29 on the shredder.

According to aforesaid method, In the priming paint (Pittsburgh, Pennsylvania) take priming paint: printing ink passes through Datacolor after the ratio of 50:1 is painted

Spectrophotometer (Lawrenceville, New Jersey) is measured the colour strength of printing ink 28 and 29.Red ink 28 shows 100% colour strength with respect to comparing red ink 29, thereby indication, with respect to the comparison red ink composition that uses the glass grinding media preparation, use the printing ink of Styrene And Chloroalkyl Acrylates base polymer grinding medium preparation to have suitable colour strength.

Average particle size distribution at the D50 place of several point in time measurement printing ink 28, and its average particle size distribution (D50) with the comparison red ink 29 that uses glass grinding media compared.Use Nanotrac particle-size analyzer (Mai Qike company, Montgomery Wei Er, Pennsylvania) to measure mean particle size.The mean particle size (D50) of printing ink 28 after 1 hour is 144.0nm, and the mean particle size after 3 hours (D50) is 134.0nm, and the mean particle size after 12 hours (D50) is 128.0nm.Compare, the D50 value of printing ink 29 is 193.0nm.These results show, compare with the ink composite that uses the glass grinding media preparation, use the ink composite of polymeric grinding media preparation can realize less D50 average particle size distribution.

Embodiment 2

Prepared and used the positively charged ion solid polymer resin as the ink composite of grinding medium.The pigment granularity descend finish after (after namely stirring or grinding), by with the pH of acid-conditioning solution so that resin, positively charged ion acid imide resin dissolves (dispersion) in ink composite.Also prepared and used glass grinding media to replace the comparison ink composite of dispersed positively charged ion solid polymer resin grinding medium.Measure and comparison property such as colour strength and size-grade distribution.

By being prepared as follows Yellow ink 30: combination 95.5g C.I. pigment Yellow 14 filter cake (44% solid; Production number 474-4480; Sun Chemical Corporation) be 30.5% with the 13.8g solids content

20001 imide resin solution (neutralize in water by acetic acid; MW=～5000; Cray Valleylad Inc., Exton (Exton), Pennsylvania), 17.0g

20001 imide resin grind resin beads, 0.2g DF-110D defoamer (air products company, Allentown, Pennsylvania) and 10.6g water.Under the Silverson mixing tank with 4400RPM with composition hash total 13 hours.Then, by adding 3.5g acetic acid with the neutralization of 2000I imide resin and being dispersed in the final composition.

With the red ink of making comparisons (printing ink 31), described yellow 14 dispersion liquids are by 29.0% pigment Yellow 14,45.7% with commercially available yellow 14 dispersion liquids

Resin solution (30% resin solid neutralizes with ammonia), 0.2%Proxel GXL sterilant, 0.2%DF-110D defoamer and 25.2% water form.Use the 1.0mm glass grinding media to replace solid imide resin grinding medium to exist Grind comparing printing ink 31 on the shredder.

Spectrophotometer (Lawrenceville, New Jersey) is measured the colour strength of printing ink 30 and 31.With respect to comparing Yellow ink 31, Yellow ink 30 shows 109% colour strength, thus indication, and with respect to the comparison Yellow ink composition that uses the glass grinding media preparation, the printing ink of use solid imide grinding medium preparation has suitable colour strength.

Measure the average particle size distribution at the D50 place of printing ink 30, and compare with the average particle size distribution (D50) of the comparison Yellow ink 31 of use glass grinding media.Use Nanotrac particle-size analyzer (Mai Qike company, Montgomery Wei Er, Pennsylvania) to measure mean particle size.Compare with the mean particle size (D50) of the 170.0nm that compares printing ink 31, the mean particle size (D50) of printing ink 30 after 13 hours is 170nm.These results show, compare with the ink composite that uses the glass grinding media preparation, use the ink composite of imide grinding medium preparation can realize less D50 average particle size distribution.

Embodiment 3

Prepared the ink composite of use vinylchlorid/vinyl acetate copolymer resin as grinding medium.After the decline of pigment granularity is finished (after namely stirring or grinding), by in composition, adding second solvent that can dissolve with dispersed copolymer, so that resin dissolves (dispersion) is in ink composite.

By being prepared as follows printing ink 32: combination 45.0g C.I. pigment Blue 15: 4 (production number 245-1539; Sun Chemical Corporation) with 75.0g3-methoxyl group-butanols, 15.0g

39000 (Lubrizol Corp.) and 30.0g85% vinylchlorid/15% vinyl acetate copolymer

H15/50 grind resin (MW=60000-80000; Wa Ke company, Calvit city (Calvert City), the Kentucky State).Under the Silverson mixing tank, mix with 4400RPM.Then, carry out the solubilising of resin by adding the 70.0g pimelinketone, in order to obtain the pigment particles dispersion liquid.

Gained granularity (D50) is 255nm.Use Nanotrac particle-size analyzer (Mai Qike company, Montgomery Wei Er, Pennsylvania) to measure the average particle size distribution at the D50 place of printing ink 32.The mean particle size of printing ink 32 (D50) is 255nm, thereby shows by using vinylchlorid/vinyl acetate copolymer resin as grinding medium, can realize the dispersion liquid of submicron particle size.

It will be apparent to those skilled in the art that in the situation that does not deviate from the subject or scope of the present invention, can modifications and variations of the present invention are.Therefore, be intended that, the modifications and variations of the present invention that provide are provided in the present invention, as long as they are in the scope of appended claims book and its equivalent.

Claims

1. method for preparing original position pigment particles dispersion liquid, described method comprises:

A kind of premix compositions is provided, and it comprises: one or more pigment, one or more dispersion agents and liquid vehicle;

In the presence of the solid abrasive agent that substantially is insoluble to described liquid vehicle, described premix compositions is ground to predetermined particle size; And

In described liquid vehicle with described solid abrasive agent solubilising.

2. method according to claim 1 is wherein implemented described with described solid abrasive agent solubilising after obtaining described predetermined particle size.

3. method according to claim 1 and 2 is wherein described with described solid abrasive agent solubilising by neutralizing to implement via pH regulator.

4. method according to claim 3, wherein said pH regulator are to add acid.

5. method according to claim 3, wherein said pH regulator are to add alkali.

6. method according to claim 4, wherein said acid is selected from acetic acid, lactic acid, phosphoric acid, hydrochloric acid or their combination.

7. method according to claim 5, wherein said alkali is selected from ammonia, mono aminoethane, triethylamine, sodium hydroxide, potassium hydroxide or their combination.

8. method according to claim 1 and 2 is wherein implemented described with described solid abrasive agent solubilising by add one or more added solvent in described premix compositions.

9. method according to claim 1 and 2 is wherein by neutralizing via pH regulator and add one or more added solvent make up to implement described with described solid abrasive agent solubilising in described premix compositions.

10. according to claim 8 or 9 described methods, wherein said one or more added solvent are organic solvent.

11. according to the described method of aforementioned arbitrary claim, wherein said solid abrasive agent comprises polymer materials.

12. method according to claim 11, wherein said polymer materials are selected from acrylate resin, methacrylate resin, cinnamic acrylic ester, acid imide resin, acrylic resin, phenoxy resin, ketone resin, urea formaldehyde, Resins, epoxy, vinyl chloride resin, rhodia resin, vibrin or their combination.

13. a printing ink, it is by the method manufacturing of aforementioned arbitrary claim.

14. according to the pigment particles dispersion liquid described in aforementioned arbitrary claim, it is used for ink-jet or non-impact printing is used.

15. according to the pigment particles dispersion liquid described in aforementioned arbitrary claim, it is used for plastics.

16. according to the pigment particles dispersion liquid described in aforementioned arbitrary claim, it is used for food.

17. according to the pigment particles dispersion liquid described in aforementioned arbitrary claim, it is used for industrial coating.

18. according to the pigment particles dispersion liquid described in aforementioned arbitrary claim, it is used for medicine.

19. according to the pigment particles dispersion liquid described in aforementioned arbitrary claim, it is used for makeup.

20. a pigment particles dispersion liquid, it is substantially free of insoluble abrasive.

21. pigment particles dispersion liquid according to claim 20, it prepares in the situation that does not have any abrasive separation mechanism.

22. an efficient method, described method is made finished product printing ink in without the situation of any abrasive separation mechanism.